The use of commercially available hyperbranched poly(ethyleneimine)s (Lupasol (TM), BASF) as polymeric modifiers in diglycidyl ether of bisphenol A thermosetting formulations using 1-methylimidazole (MI) as anionic initiator has been studied. Poly(ethyleneimine)s can get incorporated into the network structure by condensation of amine and epoxy groups. The excess, over-stoichiometric epoxy groups can undergo anionic homopolymerization initiated by MI. The thermal, dynamomechanical, and mechanical properties of the resulting materials have been determined using DSC, thermomechanical analysis (TMA), dynamomechanical analysis (DMA), and mechanical testing. The effect of the different amine modifiers on the MI networks, determined by their structure, is complex. Low initiator content and high molecular weight modifiers create significant mobility restrictions, which have a strong effect on the glass transition temperature and the apparent crosslinking density of the cured materials. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012